SCR Catalyst Management: Enhancing Operational Flexibility

2006 Megasymposium, Baltimore, MD Paper #

Scot Pritchard & Chris DiFrancesco

Cormetech, Inc., 5000 International Drive, Durham, NC 27712

Abstract
SCR Catalyst Management is an important consideration for many utilities. Many are
focused on the traditional and important considerations related to characterization of the
existing catalyst, coordination with outage planning, and basic economic factors. This
paper explores the significance of the basic steps as well as key additional operational
considerations and technology enhancements and their influence on the catalyst
management decision process. Key topics including, the impact of expanded operating
temperature range, sensitivity to ammonia:NOx distribution, enhanced NOx reduction
efficiency, limitation of SO3 emissions and enhancement of Hg emissions controls are
discussed.

Introduction
Catalyst management refers to a comprehensive methodology for predicting when
catalyst layers should be replaced or regenerated, or a new layer added, based on catalyst
deactivation rates, performance requirements, and system capabilities. Effective catalyst
management requires a long-term plan for maximizing performance based on projected
plant outage schedules, future emission regulations, available control technologies, and
plant improvements. Catalyst management strategies require evaluation of numerous
issues—boiler/SCR system operations, the plant’s and fleet’s emissions reduction
strategy, fuel management, the cost of NOx credits, outage demands, SO3 emissions
levels, mercury oxidation, capital budget considerations, etc.—with the goal of achieving
an optimal solution (Figure 1).
Traditional Considerations Additional Considerations
Fuels Impact
Catalyst Type / Regen Operation Methods
NOx, NH3 Slip, DP Fleet Considerations
Performance
Requirements & History SO3 emissions

Outage Planning/Impact Catalyst Management

Process
Hg Oxidation

Economic Factors
Optimized Solutions
Figure 1. Catalyst Management Considerations

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The process can be broken down into specific steps, facilitating its management by the
plant owner/operator (Figure 2). Each step must be considered and planned for before
determining an optimal solution for the site-specific situation.

Steps in Catalyst Management

Data Gathering Fleet Issues Assessment Catalyst Mgmt

- Boiler Operation - Outage Demands - Field Data Analysis - Ammonia Grid Tuning
- Emissions Strategy - Catalyst Interchangeability - Pilot Audit of Samples - Control Parameters
- Fuels Mgmt - Emission Credit Potential - Fuels Analysis - Operator Training
- System Inspections - Fuel Changes - What If” Scenarios - Seals & Screens
- Financial Input - SO3 Issues & Hg Oxidation - Financial Analysis - Catalyst Cleaning
- Rejuvenation
- Addition/Replacement
- Corrective Action

Catalyst Management Involves Optimizing a Wide Range of Parameters

Figure 2. Steps in Catalyst Management

Start with an inspection

To optimize the performance of its SCR system, the catalyst’s formulation, structure, and
volume are designed to take into account key parameters such as:

• Plant performance factors (such as fuel and combustion type, slagging rates,
boiler performance, air heater design, particulate collection devices, etc.).
• Operating conditions (flue gas flow rate, inlet NOx levels, temperature, the impact
of O2 and water content on catalytic potential, etc.).
• System scale-up factors (non-ideal flow distribution, temperature distribution,
ammonia-to-NOx molar ratio distribution, catalyst blockage, etc.).

If any of the above parameters varies from the initial catalyst design conditions, the life
of the catalyst may be shortened or extended. The former would be the case if, for
example, an SCR system designed to achieve a certain level of NOx reduction at a given
ammonia slip is asked to achieve a higher level of NOx reduction. Conversely, a lower
reduction level or a higher allowable ammonia slip would effectively increase the
catalyst’s useful life.

SCR system inspections and evaluations—which should be performed at least once a

year—should include physical inspections of the catalyst, reactor, and ammonia injection
system. Field performance data, including inlet NOx levels, removal efficiency,
ammonia-in-ash levels, etc. (as well as operational data such as the number of system
starts/stops, operational load range, total hours, fuel data, ash data, etc.) must be collected
and compiled to enable proper evaluation of results. Samples of the catalyst should also

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be taken to assess its catalytic potential vs. both initial design parameter expectations and
actual “as-fired” conditions.

Planning for the future

Until recently, it was possible to manage and evaluate SCR systems in a fairly stable
assessment environment. Recently, however, changes in the U.S. generation industry’s
operating environment have accelerated. The new landscape includes variables such as
seasonal market demands, the impact of flue-gas desulfurization system operation,
mercury emissions requirements, particulate and opacity limitations, the value of NOx
credits, greater need for cycling operation, fuel variability/flexibility, etc. These issues
impact catalyst management both alone and in concert.

One way to assess catalyst activity and measure it against the design deactivation curve is
to perform pilot performance tests in a laboratory. Such tests audit the catalytic potential
of an SCR catalyst (system and/or layer) by measuring the performance of a field catalyst
sample that has been in operation for a known duration. Because the tests are conducted
in a controlled environment free from scale-up factors, they allow accurate comparisons
of field sample’s catalytic potential to that of a fresh catalyst.

The deactivation rate is determined by comparing the change in catalytic potential vs.
operating hours of the sample. Measured field performance and characteristics of the fuel
fired during the operating period under evaluation are obtained from the plant and used in
conjunction with pilot test results to determine the actual unit scale-up factors and
assignable causes for measured catalyst potential. This knowledge significantly improves
the accuracy of future catalyst performance predictions.

Pilot testing and audits of catalyst activity though laboratory analysis of catalyst samples
can provide insight into methods for extending catalyst life. Regular catalyst inspection
and sampling can identify potential problems and also provide information on
deactivation causes and its prevention. Such tests also provide current data to assess SCR
system performance with the flexibility of determining a wide range of “what-if”
scenarios. Accordingly, such testing is a required first step in devising an effective
catalyst management strategy. Table 1 illustrates some of the tests commonly performed
to analyze catalyst activity and predict future catalyst performance.

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Table 1: Testing Programs for Measuring & Assessing Catalytic Activity/Potential
Test Analysis objective
Catalyst Activity Test Such tests determine the catalyst activity under
specific plant or standard conditions utilizing
representative size catalyst samples
• SO2/SO3 conversion rate, Pressure drop p,
Initial activity K0, Actual activity K, etc.
Physical Properties Test Such tests evaluate physical properties such as
catalyst surface area and porosity
Chemical Composition Test Such tests evaluate the impact of coal and ash
properties on catalyst design and performance.
These include tests such as:
• Electron Spectroscopy for Chemical Analysis
(ESCA) that determine catalyst surface
chemical composition
• Semi-Quantitative Spectrographic Analysis that
analyzes change in chemical composition.
• X-Ray Diffraction that determines the
crystalline phase of catalyst may be used in
evaluating the chemical composition of
catalysts.

A thorough understanding of the specific test conditions avoids producing erroneous or

misleading results. Common mistakes include use of inappropriate concentrations of NOx
and SOx, data evaluation under non-equilibrium conditions, and the use of non-
representative samples. The European VGB guideline attempts to address some of these
issues. However, because specific supplements are still required to achieve valid test
results, turning to a qualified laboratory and/or service providers is essential to ensuring a
proper evaluation.

Analyzing the data

Variations in fuel characteristics can have a considerable impact on catalyst life. The
nature of the fuel fired (be it Powder River Basin or eastern bituminous coal, petcoke, or
blends of both) will dictate in large part the rate of catalyst deactivation. Historical data
and know-how are key to an accurate assessment of what to expect in the future. Analytic
tools such as the one shown in Figure 3 are invaluable in assessing a fuel’s impact on a
catalyst’s long-term effectiveness.

Once catalyst testing and data evaluation are complete, the catalyst’s activity potential is
assessed in combination with field data and the future operating considerations described
in the previous section; the goal here is to determine the available catalyst-management

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options. Figure 4 is an example of a catalyst management plan that can take into account
a wide range of influences on catalyst management decisions.

Generally, there are three catalyst-management options that may be used alone or in
combination: system optimization, catalyst addition/replacement, and catalyst
rejuvenation.

Figure 3. F.I.E.L.D. Guide TM

Catalyst Management Plan Rate of catalyst

2 Initial Plus 1 Spare Layer deactivation depends
on fuels and position
of layers
1.4 7.0
(K/AV)

1.2 6.0
K/Ko

1.0 5.0
NH3 Slip, ppmvdc
Potential

Threshold moves based

Cat.Potential,

0.8 4.0
on performance
0.6 3.0 requirement and
Catalyst

0.4 2.0
system capability
Relative

0.2
Interaction w/ outage plan 1.0
Level of performance
0.0 0.0 increase depends on
0 10000 20000 30000 40000 50000 60000 70000 80000 90000 100000 needs and methods i.e.
Hours of Operation SO2 conv., higher SA,
Catalyst Potential 90%; 2 ppm Slip Threshold 90%; 4 ppm Slip Threshold higher activity, etc.
85%; 4 ppm Slip Threshold NH3 Slip, ppmvdc

Figure 4. Catalyst Management Plan

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System optimization
The purpose of ammonia injection grid (AIG) tuning is to ensure an even ammonia-NOx
molar ratio distribution to the catalyst. Contrary to popular belief, the goal of doing so is
not necessarily to get the outlet NOx profile flat; this is possible only when the inlet
profile is flat. If the inlet profile is skewed, there are generally two options:

• Tune the AIG to match the inlet distribution over the load range. In this case, the
outlet NOx profile will not necessarily be flat.
• Attempt to flatten the distribution through mixing technology.

The level of AIG tuning will depend upon the system design and operational
methodology. Proper AIG tuning/NH3:NOx distribution ensures maximum system
efficiency and reduced ammonia slip and can effectively extend catalyst life. The process
also eliminates localized regions of high ammonia slip, which can lead to air preheater
fouling when combined with SO3. Evaluation tools such as that shown in Figure 5 are
utilized to evaluate the impact of varying NH3:NOx distribution on local slip and
maximum removal efficiency capability.

Specific tests can be conducted to facilitate tuning the AIG until it is operating at peak
performance. Periodic checking and optimization of the ammonia-to-NOx distribution are
essential for ensuring the long-term optimal performance of an SCR system. The
frequency of tuning is dictated by unit-specific conditions, including NOx distribution
from the boiler and the style of AIG/mixer system in use. In general, it is worthwhile to
check the distribution annually.

NH3:NOx Distribution Analysis v s. Perform ance

100% 20

90% 18
Weighting function % and Removal

80% 16
Ammonia Slip, ppm

70% 14
Efficiency %

60% 12
efficiency
50% 10 distribution
slip
40% 8

30% 6

20% 4

10% 2

0% 0
0.7000 0.8000 0.9000 1.0000 1.1000
N H 3:N Ox Molar R atio

Figure 5. Evaluation of NH3:NOx Distribution

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Flow modeling and catalyst operating limitations are also important aspects in the initial
design of an SCR system. Over time, these considerations may influence the performance
life, range of operation, and effective cost of the system. Specific areas where additional
testing and/or evaluation may be warranted for system optimization include:

• Testing for expansion of operating temperature range to allow use of the SCR at
lower loads, thus avoiding the cost associated with “lost” NOx reduction.
• Flow modeling for evaluation of LPA (large-particle ash) mitigation methods.
• Flow modeling for AIG/mixing optimization.

Catalyst Addition or Replacement

The key to managing catalysts effectively is to determine an optimum catalyst
replacement/addition plan (i.e., when a catalyst should be replaced or an additional layer
added). As discussed, the key factors of this assessment include performance audits that
analyze the remaining potential of the catalyst. The remaining life of the field catalyst,
analyzed in conjunction with the operating history and projected use of the SCR, outage
schedule and economic/financial factors, are used to decide what catalyst action should
take place.

In most cases, SCR catalyst reactors were built with at least one spare layer. Utilization
of this layer generally results in the best economic option for utilities due to the
significant life benefit provided, vs. removing and regenerating a layer. Therefore, for
most utilities catalyst additions will be the first action followed by replacements or
rejuvenation. Because catalyst layers will deactivate at different rates depending upon the
fuel fired, the information dictating which layer should be replaced will be generated
from the performance audit, which may also be potentially applied to other fleet units
considered at the time.

An important step to include in this decision process is associated with catalyst

advancements available at the time of need. For example, in units that have either a large
pitch or a short catalyst length, there is substantial opportunity to improve the
performance potential of the unit. This may be important when considering issues such as
the value of eliminating the cost associated with an SCR catalyst action during a planned
outage, generating NOx credits, and—in some cases—meeting a mercury emissions-
reduction goal.

Transitioning to an alternate product can be done in a staged and qualified manner to

minimize any risk of a wholesale change in the catalyst. Alternately, this method may be
used to reduce the cost of the purchased catalyst by taking advantage of the performance
benefit through reduced volume. In either case, catalyst advancements should be an
integral part of the management planning process. In some cases, they can provide more
than a 50% performance enhancement or cost reduction, compared to installing a new
layer of the original catalyst.

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Case in point: the TVA Allen Plant represented a unique challenge for catalyst
management due to its two layer catalyst limitation and because the units were built
without an SCR bypass, thereby operating on a year-round basis. The units started with
an 8.2 mm pitch Cormetech honeycomb catalyst. Keeping in mind potential future use
and resulting catalyst management cost savings, the 7 mm product was also qualified
during the initial design and installation. In the second year of service, after
approximately 16,000 hours of operation, catalyst life-cycle planning was
required. Numerous options were investigated ranging from in-kind replacement to in-
situ washing, external washing, and rejuvenation. The solution involved an in-situ
replacement (patent pending) of the 8.2 mm pitch product with an extension of the pre-
qualified 7 mm pitch product (patent pending). The same process has been successfully
carried out on all 3 units over the last 18 months.

Rejuvenating a catalyst
Cleaning can be a highly effective catalyst performance recovery method in plants where
excessive accumulation of particulate matter is affecting emissions performance and
increasing draft loss. Cleaning refers to removal of physical restrictions due to buildup of
LPA or popcorn ash, and/or flyash that blocks flue-gas access to the catalyst surface.
Cleaning methods can be dry or make use of an aqueous solution. Cleaning may be done
in-situ, on-site, or off-site.

The dry method of cleaning typically involves a combination of vacuuming and air
lancing to remove the ash from the reactor; in gas applications, it also may include
removal of insulation debris and/or rust scale. This process is typically very effective
where the modules have flyash buildup but no LPA in the catalyst. This can be performed
in-situ or off-site, depending on site logistics and outage considerations.

Wet cleaning of severe ash buildup on a catalyst cleaning is referred to as washing,

regeneration, or rejuvenation, depending upon the process and aqueous solution used.
This is a more elaborate cleaning process that removes most of the chemical buildup on
the catalyst surface. The process generally restores the catalyst activity lost to both gross
and fine physical blockage. In addition, the process can be used to restore all or a portion
of the catalytic activity lost due to chemical poisons.

Generally, the regeneration process consists of the following steps:

1. Baseline testing of the catalyst to assess performance recovery.

2. Blowing and vacuuming ash off the catalyst.
3. Adding ultrasonic energy, bubbling air in the solution and/or physically moving
the module to remove any remaining ash.
4. Washing the catalyst module using a cleansing solution. This may need to be done
multiple times, with different solutions, in accordance with the system vendor’s
recommendations.
5. Drying each catalyst module using forced hot air.
6. Testing the catalyst elements to verify that the cleaning has met the established
goals. 3. Washing using a
cleansing solution

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Regeneration/cleaning must be considered at every plant where the condition of the
catalyst condition and its remaining service life dictate it. If it is determined to be
economically advantageous to the plant, catalyst cleaning can extend the active life span
of a catalyst and be an essential part of 4.a Bubbling
catalyst& aeration
management program for a plant. In all
cases, the process should be pre-qualified on samples
under pressure prior to implementation of the full-
2. Vacuuming
scale process. Items for consideration include the level of activity recovery (physical or
chemical), the impacts on SO2 conversion and mercury oxidation, cost, schedule, and any
applicable warranty conditions.

Key Additional Considerations

There are many additional considerations involved in the process of catalyst

management. Many are utility, plant specific, and/or unit specific. Three topics of
particular significance are 1) Expansion of allowable operating temperature range, 2) Hg
oxidation, and 3) Limitation of SO3 emissions.

1) Expansion of allowable operating temperature range – Traditional techniques for

dealing with low temperature operation of SCR catalyst include a) load limiting i.e.
restrict unit operation to a load which maintains SCR inlet temperature above Ammonia
BiSulfate (ABS) formation, b) Install and utilize flue gas temperature control i.e. burner,
gas-side bypass, or water side bypass.

The temperature at which ABS forms is a function of the concentration of water vapor,
SO3 and NH3. Under the proper conditions ABS will condense in the catalyst pores
masking of active catalytic sites, thus limiting SCR catalyst potential to reduce NOx
(Figure 6).
(ABS)
[NH3(g) + SO3(g) + H2O(g) NH4HSO4(l)]

PABS = PNH3 PSO3 PH2O = 1/K

T > Dew Point T < Dew Point

NH3 NH3 NO NH
Bulk Gas Flow NO NO H2O H2O Bulk Gas Flow NO NO 3

N NH3 NO H2O N2 H O
NH3 NO H2O 2 H2O 2
N NO N2 NH3
NO N2 2 H2O NH3
NH3 NH3 O NO H2O
NH3 N2 H2O
O2 2

Catalyst Pore

Active Surface Layer Liquid ABS

Figure 6. Pore Condensation of ABS

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Many units installed economizer bypass systems to maintain SCR inlet temperature,
others evaluated the associated capital, operating, and maintenance expense and decided
to increase the minimum load specification in order to maintain temperature. Both of
which can present either direct or indirect expense to the utility.

Based on a need presented to by one of it’s customers to expand the operating

temperature range of their SCR, Cormetech focused on phenomenon which restricted
operation, namely formation of ABS in the catalyst, and methods to assess performance
impacts and risks. Subsequent to this investigation, it was found that many utility clients
had a need/desire to expand the operating temperature range of the SCR to take
advantage of generation of generation of NOx credits and/or reduction NOx emitted
against a cap. Based on this need, Cormetech continued fundamental work in this area to
expand the capability to advise clients on optimizing the SCR operating range.

The basic process includes an understanding of the catalyst performance as a function of

its available catalyst pore structure, principles of pore condensation, and boiler
operational goals in terms of NOx reduction and time, as well as the limitations,
including SO3 emissions, recovery temperature, ramp rate, control logic options, etc.
Results from specific investigations have generated significant savings (> $2MM
annually) related to the value of NOx and or allowed more effective utilization of system
wide generating units.

2) Hg Oxidation – SCR catalyst will oxidize mercury to varying degrees based on a wide
variety of inputs including catalyst type, NH3 concentration, temperature, HCl
concentration, etc. The basic reaction process is described in Figure 7.

NO + NH3 + 1/4 O2 N2 + 3/2 H2O (NOx Reduction)

Hg + 2 HCl + ½ O2 HgCl2 + H2O (Hg Oxidation)
HgCl2 + NH3 + ¼ O2 Hg + 2 HCl + ½ N2 + ½ H2O (HgCl2 Reduction)

Figure 7. General SCR Chemistry for Hg Oxidation

Use of the SCR in combination with a wet Flue Gas Desulfurization (FGD) system can
be an effective method for meeting Hg emission limits. Cormetech has worked with

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industry partners, EPA, and utilities over the last 3 to 4 years to develop and demonstrate
know-how related to predicting and guaranteeing the level of Hg oxidation through it’s
SCR catalyst. Figure 8 shows an example of actual field performance versus predictive
models for aged SCR catalyst.

Predicted vs. Actual SCR Hg - Large Utility Unit at

Full Load After Several Ozone Seasons

100
Predicted
Outlet Hg+2, %

90
Actual (4-test
80
avg.)
70 Individual Tests

60
0 10 20 30 40 50 60
HCl(g), ppmvd

Figure 8. Full Scale Hg Oxidation Results on Aged SCR Catalyst

Use of information developed to date regarding Hg oxidation capabilities will be

combined with the more traditional SCR catalyst management decision making process
as outlined in figure 4 to assist utilities to optimize catalyst management.

3) Limitation of SO3 emissions - Historically, minimizing SO2 conversion while

maintaining high levels of NOx reduction were in conflict, and in some cases could not
be achieved. Therefore, Cormetech focused on developing additional catalyst product
features to minimize SO2 conversion while maintaining high catalyst activity yielding
high NOx reduction capability with low ammonia slip. The product extension utilizes
advanced extrusion, product and materials know-how in combination with a well proven
product base. The performance enhancement can, in some cases, achieve less than 0.1%
SO2 oxidation while maintaining all other key product performance and durability
features. Use of the advanced SCR product may be exclusive or combined with other
SO3 mitigation techniques including; fuel switching, in-furnace mitigation with reagent,
and pre/post APH mitigation with reagent.

The superior performance of the low SO2 conversion catalyst relative to a conventional
catalyst is because of greater open area, thinner wall thickness, improved composition
and geometry for strength. The design is optimized to reduce volume, pressure drop and
SO2 oxidation rate. Table 2 outlines some of the performance characteristics of the new
product in comparison to the conventional catalyst in terms of relative catalyst volume,

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pressure drop and SO2 oxidation. Two cases are shown to illustrate the alternative
methods for utilizing the features of the high open are product.

Table 2: Advanced SO2 Conversion Catalyst Performance Summary

Product Case 1 Case 2
Relative
Relative Relative Relative SO2
Opening GSA Volume Pressure Volume Oxidation
Product Pitch (mm) (m2/m3) Required Drop Required Required
Conventional 7.4 6.3 445 100% 100% 100% 100%
High
Performance 6.9 6.3 539 75% 61% 100% 25%

Initial installations of Cormetech’s low SO2 conversion catalysts at full reactors with
< 0.5% SO2 conversion were designed in 2002 and installed in 2003 and continue to
operate successfully. Subsequent individual layer additions of the low SO2 conversion
catalyst have been designed and installed with conversion rates of less than 0.1%. A base
installation exceeding 40,000 MW of coal fired units in the U.S. utilize a form of the high
open area/high performance product. An additional 5,500 MW, 2,000MW of which are
in operation are applying another extension of the technology to achieve greater overall
SCR performance at lower SO2 conversion.

Conclusion
SCR Catalyst Management presents a diverse and complex issue for many utilities. The
US industry is now approaching the time in which significant catalyst management
decisions will be made as layer additions/replacements and new installations are required
in order to maintain performance and/or achieve new regulatory challenges. The SCR
catalyst and system has a significant impact beyond just NOx reduction which must be
considered in the decision making process. Cormetech has unique knowledge and
capability to assist utilities to evaluate and optimize the SCR catalyst management
process to achieve performance goals in NOx reduction, Hg oxidation, SO3 emissions,
and operation flexibility.

Key Words
Selective catalytic reduction, catalyst management, SO3, mercury oxidation, operating
range, AIG tuning.

Related Papers/Articles
Power Magazine Vol 150 No. 1 – Long Term Catalyst Healthcare
Power Engineering Magazine May 2006 – Improved Catalyst can Clean the Air
ICAC Conference 2005 - Effects of SCR Catalyst and Wet FGD Additive on the
Speciation and Removal of Mercury within a Forced-Oxidized Limestone Scrubber

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